CN105683260A - Polyvinylidene fluoride resin particles and method for producing same - Google Patents

Abstract

A method for producing polyvinylidene fluoride resin particles which is characterized by involving the execution of: a step (a1 step) for adding a solution containing 75-99 mass% of an organic solvent, 1-25 mass% of water, and 0.5-15 mass% of a polyvinylidene fluoride resin, given that the total content of the organic solvent and the water is 100 mass%, to a poor solvent of the polyvinylidene fluoride resin, and causing polyvinylidene fluoride resin particles to precipitate therefrom; and a step (a2 step) for causing polyvinylidene fluoride resin particles to precipitate from the solution by flash crystallization. Consequently, it is possible to produce polyvinylidene fluoride resin particles using a simple operation capable of being executed industrially and without including a surfactant.

Description

Poly-1,1-bis-fluoroethylene resin particle and manufacture method thereof

Technical field

The present invention relates to poly-1,1-bis-fluoroethylene resin particle and its manufacture method.

Background technology

Below, by poly-1,1-bis-fluoroethylene resin (sometimes referred to as " PVDF resin ". ) particle that formed has the characteristics such as excellent weathering resistance, stain resistance, solvent resistance, water tolerance, wet fastness, the anti-fouling material being suitable as in printing press, toning agent purposes, weathering resistance, water tolerance coating resin.

As the manufacture method of PVDF resin particle, report and make fluorine resin be dissolved in polar organic solvent, then this solution is fed in water, thus make the method (patent documentation 1) of the particle of particle diameter hundreds of μm～number mm; The coating Stock solutions comprising fluo-copolymer etc. is carried out spraying dry and obtains the method (patent documentation 2) of the particle of particle diameter number 10 μm; Under the coexisting of fluorine system tensio-active agent and nonionic system tensio-active agent, the monomer mixture making vinylidene fluoride monomers or comprise vinylidene carries out letex polymerization, manufactures the method (patent documentation 3) etc. of the aqueous liquid dispersion of the PVDF resin particle comprising below particle diameter 200nm.

Propose the manufacture method of PVDF resin particles some like this, but only by PVDF resin dissolves in good solvent, this solution is injected into the method for the poor solvents such as water or carries out in spray-dired method, only obtain several 10 μm～number mm particle. In addition, in order to obtain the particle of below 200nm, it is necessary under the existence of tensio-active agent, vinylidene fluoride monomers is carried out letex polymerization, about such particle, due to needs tensio-active agent, therefore not necessarily sufficient in order to obtain really pure PVDF resin particle. Particularly, in the field needing battery of future generation important in the medical field of its purity, electronic information field and new forms of energy, surfactant-free is one of the most important problem.

If electronic information material, medical material etc. use the PVDF resin particle manufactured by letex polymerization, then according to circumstances, sometimes performance is brought detrimentally affect by tensio-active agent, therefore emulsifier-free emulsion polymerization is developed as the particle manufacturing process (non-patent literature 1,2) not using tensio-active agent, for liquid crystal spacer, electroconductive particle, manifolding toning agent, medical examination carrier etc. But, the example being synthesized PVDF resin particle by emulsifier-free emulsion polymerization is not yet reported.

On the other hand, known use in electronic information material field coating material, in film etc., filming is accelerated, and uses particulate to be effective with precursor forms when the film used in these fields is formed, but the particle diameter requiring the particle wherein used is less than 1 micron.

From such situation, it is desirable to exploitation is containing tensio-active agent, simple and easy and manufacture the method for the PVDF resin particle of the consistent particle diameter of particle diameter less than 1 micron in a large number.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-177614 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2003-82295 publication

Patent documentation 3: Japanese Unexamined Patent Publication 7-90153 publication

Non-patent literature

Non-patent literature 1: Japan rubber association will 2006 (79) 61

Non-patent literature 2: " the state-of-the-art technology trend of polymer particles (the Port リ up-to-date skill of マ micropartical to) " 2008, (strain) east レ リ サ チ セ Application タ

Summary of the invention

Invent problem to be solved

The problem of the present invention is by not containing tensio-active agent, industrial can implement, and the operation of simplicity manufactures PVDF resin particle.

For solving the method for problem

The present inventor etc. conduct in-depth research to solve above-mentioned problem, result finds that the PVDF resin solution of the organic solvent by comprising water is added into substantially not containing in the poor solvent of the PVDF resin of tensio-active agent surprisingly, or carry out flash distillation crystalline substance analysis, thus obtain fine and that particle diameter is consistent PVDF resin particle stablely, thus complete the present invention.

Namely, the present invention relates to a kind of poly-1, the manufacture method of 1-bis-fluoroethylene resin particle, it is characterized in that, implement a1 operation or a2 operation, described a1 operation is the organic solvent by comprising 75～99 quality % relative to the total amount 100 quality % of organic solvent and water, the water of 1～25 quality % and poly-the 1 of 0.5～15 quality %, the solution of 1-bis-fluoroethylene resin is added into poly-1, in the poor solvent of 1-bis-fluoroethylene resin, make poly-1, the operation that 1-bis-fluoroethylene resin particle precipitates out, described a2 operation makes poly-1 by flash distillation crystalline substance analysis, the operation that 1-bis-fluoroethylene resin particle precipitates out from above-mentioned solution.

In the present invention, it is possible to implement a1 operation and a2 operation. Such as in a2 operation, above-mentioned solution is added in the poor solvent of PVDF resin and carries out flash distillation crystalline substance analysis, such that it is able to implement a1 operation and a2 operation simultaneously.

The effect of invention

If use the present invention, then can easy and stable ground process industry is difficult to stable acquisition substantially containing tensio-active agent, the PVDF resin particle of average 1 below particle diameter 300nm particularly below 200nm, it is provided that widely useful material in industry. the PVDF resin particle obtained by the present invention can be suitable for being coated with solidification forming material, rapid shaping/quick manufacture material, plastisol is with sticking with paste resin, powder adhesion material, the mobility improvement material of powder body, lubricant, rubber ingredients, abrasive, thickening material, filter agent and flocculating aids, jelling agent, agglutinant, additive for coatings, oil absorber, releasing agent, the sliding improving agent of plastic film/sheet, anti blocking agent, gloss conditioning agent, delustring treatment agent, light diffusing agent, surface high rigidity improving agent, tackiness agent material, caking agent, coating agent, the valve of semi-conductor and/or liquid crystal manufacturing installation and/or lid, guide rail, roller, bolt, liner, toughness improves the various properties-correcting agent such as material, liquid crystal indicator spacer, chromatographic grade fills material, the retention agent of spices/agricultural chemicals, chemical reaction catalyzer and carrier thereof, adsorbent, Ceramic manufacturing sintering material, the standard particle measuring/analyzing, the particle of field of food industry, powder coating material, electronic photo developing toner, lithium secondary battery dividing plate caking agent etc.

Accompanying drawing explanation

Fig. 1 is the scanning electron microscope image of the PVDF resin particle that the method that display is related to by one embodiment of the present invention manufactures.

Fig. 2 is the scanning electron microscope image of the PVDF resin particle that the method related to by conventional art manufactures.

Embodiment

Hereinafter, embodiments of the present invention are described in detail.

[the PVDF resin of raw material]

So-called PVDF resin in this specification sheets, refers to the resin polymerization of 1,1-bis-vinyl fluoride obtained, refers to the material shown in following general formula (1).

As PVDF resin, commercially available product can be used, as concrete commercially available PVDF resin, can enumerate such as, KF polymkeric substance W#1100, #1300, #1700, #7200, #7300, #8500, #9100, #9200, #9300 ((strain) Network レ Ha society system), カ イ Na 721, 741, 761, 461, 301F, HSV900, カ イ Na Off レ ッ Network ス 2851, 2801, 2821 (ア Le ケ マ (strain) society system), ソ レ Off 1013, 1015, 21216, 31508, 6020 (ソ Le ベ イ ス ペ シ ャ リ テ ィ Port リ マ ズ ジ ャ パ Application (strain) society system), シ グ マ ア Le De リ ッ チ ジ ャ パ Application contract commercial firm reagent etc.

In addition, PVDF resin can be the homopolymer of poly-1,1-bis-vinyl fluoride, or in the scope of characteristic not damaging PVDF resin, it is possible to for not containing the multipolymer of other monomer component gathering 1,1-bis-vinyl fluoride. as not containing poly-1, other monomer component of 1-bis-vinyl fluoride, if illustrated, can be and ethene then, propylene, iso-butylene, the hydrocarbon system vinyl monomers such as divinyl, ethylene fluoride, borontrifluoride ethene, the fluorine system vinyl monomers such as tetrafluoroethylene, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, toxilic acid methyl esters, ethyl maleate, Malaysia acid butyl ester, vinylformic acid 2-carboxyethyl, methacrylic acid 2-carboxyethyl, acryloxy ethylsuccinic acid, methacryloxyethyl succsinic acid, acryloxy ethyl phthalic acid, methacryloxyethyl phthalic acid, the monomer containing carboxyl ester group such as trifluoromethyl acrylate, vinylformic acid, methacrylic acid, toxilic acid, the monomer containing carboxyl such as monomethyl maleate, vinyl-acetic ester and saponified, propionate and saponified, vinyl butyrate and saponified etc. multipolymer thereof. wherein, from the view point of improve the cementability of PVDF resin, it is preferably the vinylformic acid 2-carboxyethyl as the monomer component with carboxyl, methacrylic acid 2-carboxyethyl, vinylformic acid, methacrylic acid, toxilic acid, monomethyl maleate etc., from the easiness obtained of industry, more preferably vinylformic acid, methacrylic acid, toxilic acid, monomethyl maleate etc., it is particularly preferred to be toxilic acid, monomethyl maleate etc.

About the copolymerization amount of such multipolymer, as long as the scope not damaging the characteristic of PVDF resin is just passable, when the total of Component units is set to 100mol%, for below 30mol%, it is preferably below 25mol%, it is more preferably below 20mol%, more preferably below 10mol%, it is particularly preferred to be below 5mol%.

The lower limit of the weight-average molecular weight of PVDF resin is more than 1,000, it is preferable to more than 5,000, it is more preferable to be more than 10,000, more preferably more than 50,000, it is particularly preferred to be more than 100,000.

In addition, the weight-average molecular weight of PVDF resin is less than 10,000,000, it is preferable to less than 5,000,000, more preferably less than 3,000,000.

In addition, the weight-average molecular weight of the so-called PVDF resin in this specification sheets, refers to that the gel permeation chromatography (GPC) by dimethyl formamide is used as solvent measures, is converted into the weight-average molecular weight of polystyrene.

As PVDF resin, the PVDF resin become by known method manufacture before letex polymerization, precipitation polymerization, suspension polymerization etc. can be enumerated, particularly from the view point of the usage quantity of tensio-active agent can be suppressed, it is preferable to the PVDF resin manufactured by precipitation polymerization. The form of PVDF resin does not have special stipulation, if specifically illustrated, then can enumerate powder body, particle, bead (pellet) etc. From the view point of operability described later is with shortening the time required for dissolving, it is particularly preferred to be the PVDF resin of powder.

[manufacture of PVDF resin particle]

The PVDF resin solution comprising the organic solvent with water blending and water can be manufactured by the PVDF resin particle in present embodiment via arbitrary operation of following (a1 operation) or (a2 operation).

[precipitation operation]

(a1 operation) is to substantially not making, containing the poor solvent interpolation PVDF resin solution of tensio-active agent, the operation that PVDF resin particle precipitates out

(a2 operation) does not substantially make, containing PVDF resin dissolves liquid carries out in the poor solvent of tensio-active agent flash distillation crystalline substance analysis, the operation that PVDF resin particle precipitates out

First, make PVDF resin dissolves in organic solvent. Here, the PVDF resin particle of target is being used for the situation etc. of water soluble paint etc., the corrosion etc. of the device caused to prevent the mineral ion owing to coexisting, it is particularly preferred to use the powder PVDF resin not containing mineral ion.

As long as PVDF resin is carried out the solvent dissolved by the organic solvent that the dissolving of PVDF resin uses, and with the solvent of water blending. specifically, can enumerate from METHYLPYRROLIDONE (following, sometimes referred to as NMP) etc. N-alkyl pyrrolidone class, 1, 3-dimethyl-2-imidazolone is (following, sometimes referred to as DMI) etc. ureas, N, N-N,N-DIMETHYLACETAMIDE is (following, sometimes referred to as DMAc), N, dinethylformamide is (following, sometimes referred to as DMF) etc. chain shape acid amides series solvent, methyl-sulphoxide is (following, sometimes referred to as DMSO), dimethyl sulfone, the oxysulfide system polar solvents such as tetramethylene sulfone, acetone, the ketone series solvents such as methyl ethyl ketone, acetonitrile, the at least one solvent selected in the nitrile series solvents such as propionitrile. wherein, from the handling easiness of the stability of solvent and industry, it is preferable to NMP, DMI, acetone, methyl ethyl ketone, acetonitrile, it is more preferable to be NMP, acetonitrile.

About the atmosphere of dissolving tank, in order to suppress decomposition, the deterioration of PVDF resin, operate safely to carry out further, it is preferable that oxygen concentration is reduced, it is preferable that under non-active gas atmosphere, configure dissolving tank. As non-active gas, nitrogen, carbon dioxide, helium, argon gas etc. can be enumerated, it is contemplated that to economy, obtain easiness, it is preferable to nitrogen, argon gas, carbon dioxide, it is particularly preferred to use nitrogen or argon gas.

Dissolving method is not particularly limited, and when making PVDF resin solution, adds PVDF resin, organic solvent and water, stir and dissolve in the container of regulation. At normal temperatures in undissolved situation, by carrying out heating and dissolve.

Can by PVDF resin dissolves after organic solvent, add water. Add in the method for water upon dissolution, after making PVDF resin solution in the container of regulation, in PVDF resin solution, add water. The interpolation of water can use transferpump, coltfoal transfer pipet etc., if once adding a large amount of water, then PVDF resin precipitates out, and the dissolving of PVDF resin needs long-time, it is preferred to slowly add water. In order to manufacture the consistent PVDF resin particle of particle diameter, it is preferable that after making PVDF resin be dissolved in solvent completely, be added into poor solvent, or carry out flash distillation crystalline substance analysis and precipitate out, it is possible to there is undissolved PVDF resin.

The water yield added is different according to the kind of the PVDF resin concentration dissolved, organic solvent, is 0.5～40 quality % of organic solvent quality, it is preferable to 1～25 quality %. If the amount of water is very few, then generating irregular particle, if the amount of water is too much, then PVDF resin precipitates out.

Solvent temperature is different according to the kind of solvent, the concentration of PVDF resin of use, is generally normal temperature～200 DEG C, it is preferable to normal temperature～100 DEG C, or below the boiling point of organic solvent.

Dissolution time is different from concentration, the solvent temperature of the kind of solvent, PVDF resin, is generally the scope of 5 minutes～50 hours, it is preferable to the scope of 10 minutes～40 hours.

If PVDF concentration height, then PVDF resin solution to poor solvent add and when particle is precipitated out, generation particle fusion etc. each other, it is possible to can not get the particle that the little particle of particle diameter, particle diameter are consistent.

Therefore, about the usage quantity of PVDF resin when PVDF resin solution is added into the not poor solvent of PVDF resin containing tensio-active agent, usually it is below PVDF resin 15 mass parts relative to total 100 mass parts of organic solvent, water and PVDF resin, it is preferable to more than 0.1 mass parts below 10 mass parts.

If being above-mentioned scope, then can be applicable to industrial production. After making PVDF resin dissolves in above-mentioned solvent in the present embodiment, by PVDF resin solution for precipitation operation described later.

[precipitation operation]

[a1 operation]

In a1 operation, to not adding PVDF resin solution and make PVDF resin particle precipitate out containing in the poor solvent of the PVDF resin particle of tensio-active agent.

When PVDF resin solution being added into the poor solvent of PVDF resin, it is possible to be injected into or be added drop-wise to the container (hereinafter sometimes referred to " receiver ") of the poor solvent adding PVDF resin continuously from the container adding PVDF resin solution. , it is possible to PVDF resin solution is added via gas phase from poor solvent, in addition from the view point of obtain fine and that particle diameter is consistent particle, it is preferable that directly join in poor solvent.

The method of PVDF resin particle is made with poor solvent for making PVDF resin contact, there is following method: after adding PVDF resin solution to the receiver adding poor solvent and make particlized liquid, particlized liquid is taken out, for method (intermittent type) and these 2 kinds of methods of Continuous Flow general formula (sometimes referred to as continous way) of subsequent handling. The reactor that Continuous Flow general formula uses have continuous tank reactor (continuousstirredtankreactor, be called for short: CSTR) and tube-type reactor (plugflowreactor, abbreviation: PFR). For the particlized of PVDF resin, arbitrary reactor can both adapt to.

The method using CSTR is following method: add poor solvent in receiver (being sometimes referred to as reactor during continous way); after adding PVDF resin solution and producing PVDF resin particle; then; this micronize liquid drips simultaneously and adds PVDF resin solution and poor solvent; take out the particlized liquid of PVDF resin simultaneously from receiver continuously, carry out continuously the method for particlized., it is also possible to drip in the particlized liquid of the PVDF resin made by intermittent type simultaneously and add PVDF resin solution and poor solvent, in addition take out the particlized liquid of PVDF resin continuously from receiver and make particlized liquid simultaneously.

When using CSTR, it is necessary to PVDF resin solution and poor solvent are dripped simultaneously and adds. About the ratio of PVDF resin solution rate of addition relative to the rate of addition of poor solvent, as long as PVDF resin particle can be generated, it is not particularly limited, from productive viewpoint, the rate of addition of poor solvent is preferably between 0.1～100 relative to the ratio of PVDF resin solution rate of addition, it is more preferable to be between 0.2～50.

In addition, if the ratio that the particlized liquid weight in receiver takes out flow relative to the particlized liquid of receiver (reactor) is set to the residence time, then about the residence time, as long as fine and that particle diameter is consistent particle can be obtained, just it is not particularly limited, it is preferably between 1 second～10 hours, it is more preferable to be between 1 minute～1 hour.

In receiver, in order to keep the homogeneity of particlized liquid, it is possible to arrange mixing device. As the example of mixing device, stirring rake, double-shaft mixer, homogenizer, ultrasonic irradiation etc. can be enumerated.

Use the method for PFR be by PVDF resin solution and poor solvent with the logical liquid of certain speed to joining in pipe, pipe makes PVDF resin solution mix with poor solvent and carry out particlized joining, takes out the method for particlized liquid continuously, it is possible to use various join pipe. Such as, when using 2 to join pipe, it is also possible to by PVDF resin solution with the logical liquid of certain speed to interior pipe, by poor solvent with the logical liquid of certain speed to outer tube, PVDF resin solution is made to mix with poor solvent and carry out particlized in outer tube. , it is possible to by logical for PVDF resin solution liquid to outer tube, in addition by logical for poor solvent liquid to interior pipe.

When use 1 join pipe carry out continuous particlized, such as, when T font joins pipe, it is also possible to from the direction being 90 degree relative to PVDF resin solution stream, poor solvent is carried out logical liquid, make PVDF resin solution contact with poor solvent and carry out particlized.

Owing to various pipe of joining can be used to make PVDF resin solution mix with poor solvent to carry out particlized continuously, therefore the method for PFR is not limited to aforesaid method.

When using PFR, about the logical liquid speed of the logical liquid speed of PVDF resin solution and poor solvent, as long as PVDF resin particle can be generated, it is not particularly limited, from productive viewpoint, the logical liquid speed of PVDF resin solution is preferably between 0.1～100 relative to the ratio of the logical liquid speed of poor solvent, it is more preferable to be between 0.2～50.

In addition, the mixing portion of PVDF resin solution and poor solvent can be only and join pipe, it is possible to arrange tubulose mixing device. As tubulose mixing device, the tubulose mixing device etc. of the static mixing works such as can enumerate above-mentioned mixing device, have static mixer.

About the mixing time of PVDF resin solution and poor solvent, as long as being in same range with the above-mentioned residence time. About the internal diameter joining pipe, as long as PVDF resin solution carries out mixing with poor solvent, it does not have be particularly limited to, from productive viewpoint, it is preferable that be between 0.1mm～1m, it is more preferable to be between 1mm～1m.

When using inner and outer tubes to join pipe as 2, about the ratio of diameter of inner pipe with outer tube diameter, as long as forming particlized liquid, just it is not particularly limited, it is preferably between outer tube diameter/diameter of inner pipe=1.1～500, it is more preferable between outer tube diameter/diameter of inner pipe=1.1～100.

As the poor solvent of PVDF resin particle, ester series solvent, diethyl ether, Di Iso Propyl Ether, the tetrahydrofuran (THF)s, two such as aromatic hydrocarbons series solvent, ethyl acetate, methyl acetate, butylacetate, butyl propionate such as aliphatic hydrocarbon series solvent, benzene, toluene, o-Xylol, m-xylene, p-Xylol, naphthalene such as pentane, hexane, heptane, octane, nonane, decane can be enumeratedAlcohol series solvent, the water etc. such as the ether series solvents such as alkane, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, it is preferable to alcohol series solvent, the water etc. such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, it is particularly preferred to be methyl alcohol, second alcohol and water.

In addition, from the view point of make PVDF resin particle evenly be scattered in poor solvent, the poor solvent of PVDF resin is preferably and the solvent dissolving even the blending of the organic solvent that uses. Here what is called evenly blending, is undertaken mixing by two or more solvent even if referring to and leaves standstill 1 day and interface also do not occur. Such as, relative to water, the solvent as evenly blending such as NMP, DMF, DMAc, acetone, DMSO, tetrahydrofuran (THF), acetonitrile, methyl alcohol, ethanol can be enumerated.

In addition, about the poor solvent of PVDF resin, as long as with organic solvent evenly the blending used in dissolving, then can use single solvent, the solvent that can also be mixed with two or more, particularly from being easy to obtain fine and that particle diameter is consistent particle aspect, it is preferred to use the mixed solvent etc. of water-ol class, water-nitrile class comprises the mixed solvent of water.

The usage quantity of the poor solvent of PVDF resin is not particularly limited, it is possible to illustrate relative to dissolving the scope that solvent 1 mass parts used is 0.1～100 mass parts, it is preferable to 0.1～50 mass parts, more preferably 0.1～10 mass parts.

The poor solvent precipitating out in operation the PVDF resin used is not substantially containing tensio-active agent. Most preferably completely not containing particle surface promoting agent, it is also possible to be mixed into not damage the degree of the effect of the present invention. Specifically, relative to the quality of PVDF resin, the ratio that is mixed into of tensio-active agent to be limited to below 3 quality %, will be limited to as far as possible and be less than 1 quality %.

Receiver temperature when adding PVDF resin solution in the poor solvent of PVDF resin can be set as below the boiling point of more than 0 DEG C and solvent, according to solvent used, sometimes there is particle fusion each other, can not get particle, therefore as being about to the temperature before adding, it is preferable to 0～40 DEG C. By this interpolation, PVDF resin particle precipitates out from PVDF resin solution, the liquid obtaining PVDF resin particles dispersion or the liquid suspended. In addition, when adding PVDF resin solution, it is preferable that the poor solvent of PVDF resin is stirred.

[a2 operation]

In a2 operation, the PVDF resin solution of dissolving is carried out flash distillation crystalline substance analysis and PVDF resin particle is precipitated out.

So-called flash distillation crystalline substance analysis, it is instigate that PVDF resin solution solidifies rapidly, the method for crystallization, more specifically, above-mentioned solution under making to be in heat/pressure via nozzle or under pressurization is ejected in other container (hereinafter sometimes referred to receiver) of below below the pressurized pressure of below the boiling point of the organic solvent that dissolving uses (can be below normal temperature) (can be under decompression) or pressurized pressure (can be under decompression) and carries out shifting liquid so that it is the method for crystalline substance analysis.

When carrying out flash distillation crystalline substance analysis, it is preferable that spray PVDF resin solution in poor solvent.The preferably flash distillation when the poor solvent to receiver side is put in the front end of the nozzle sprayed by PVDF resin solution, but spray nozzle front end can also be separated with poor solvent, via gas phase, flash distillation is in poor solvent.

If specifically described, then preferably by under being held in heat/pressure or the lower container of pressurization towards the receiver ejection PVDF resin solution of (can under decompression) under normal atmosphere, to carry out, flash distillation is brilliant analyses. Such as in above-mentioned dissolution process, if heating in the pressure vessels such as autoclave, dissolving, then becomes pressurized state (can be pressurizeed further) by non-active gas such as nitrogen from superzapping due to what cause by heating in container. Bleed off pressure from this state and receiver being discharged into normal atmosphere, such that it is able to further carry out easily. In addition, when dissolving at normal temperatures, it is possible to by dissolving tank being forced into arbitrary pressure, in the poor solvent of PVDF resin, carry out flash distillation crystalline substance analysis, such that it is able to obtain PVDF resin particle.

As the poor solvent used when carrying out flash distillation crystalline substance analysis in poor solvent, it does not have limit especially, it is possible to use the poor solvent same with poor solvent illustrated in a1 operation.

The usage quantity of the poor solvent of PVDF resin is not particularly limited, it is possible to illustrate relative to dissolving the scope that solvent 1 mass parts used is 0.1～100 mass parts, it is preferable to 0.2～50 mass parts, more preferably 0.3～10 mass parts.

As operational condition during flash distillation crystalline substance analysis, the container below the pressure that the scope that the solution that the scope in normal temperature～200 DEG C, preferably normal temperature～100 DEG C is dissolved is stated afterwards usually can be adopted pressurized or under decompression carries out with 1 section the method for flash distillation crystalline substance analysis; Or than the container that pressure is low in the groove adding lysate carries out the method etc. of flash distillation crystalline substance analysis with multistage. Specifically, such as, in above-mentioned dissolution process, if heating in the pressure vessels such as autoclave, dissolving, then becomes pressurized state (can be pressurizeed further) by non-active gas such as nitrogen from superzapping due to what cause by heating in container. Make this lysate becoming pressurized state carry out flash distillation towards the receiver of the normal atmosphere of the poor solvent adding PVDF resin, or carry out flash distillation towards the receiver under decompression. In addition, the pressure vessels such as autoclave do not heat and dissolved, the lysate making to be forced into arbitrary pressure and become pressurized state carries out flash distillation towards the receiver of the normal atmosphere of the poor solvent adding PVDF resin, or carries out flash distillation towards the receiver under decompression. The pressure (gauge pressure) of the lysate carrying out flash distillation crystalline substance analysis is preferably 0.2～4MPa. Preferably the receiver of the lysate being in this environment under normal atmosphere is carried out flash distillation crystalline substance analysis.

The temperature of receiver is different according to the poor solvent of the PVDF resin joined in receiver, it is preferably temperature～50 DEG C that the poor solvent of PVDF resin does not solidify, specifically in the case of water, the temperature before flash distillation crystalline substance analysis is carried out as being about to, it is preferable to 0～50 DEG C.

In flash distillation method for crystallization, the poor solvent of air or the PVDF resin putting into the pipe connecting outlet from dissolving tank to receiver can be enumerated, carry out the method for flash distillation crystalline substance analysis, put into poor solvent and can obtain finer PVDF resin particle, it is preferred to.

The PVDF resin particle obtained by above-mentioned precipitation operation (a1 operation), (a2 operation) can be obtained with the state of dispersion liquid or suspension.Hereinafter, the dispersion liquid of this state or suspension are sometimes referred to as flash liquid. In addition, now, when comprising when not the dissolving the coarse grain graded of PVDF resin added, it is also possible to removed by filtration etc.

By adopting the method for present embodiment, it is possible to manufacture not containing tensio-active agent, the particle that fine and granularity is consistent stablely.

[filtering/segregation operation]

As the method being undertaken emanating by PVDF resin particle, the known solid-liquid separating methods such as filtration, centrifugation, centrifuging can be adopted to carry out, but in order to such for average 1 below particle diameter 300nm fine PVDF resin particle being emanated with carrying out high-level efficiency by solid-liquid separation operation, expect to be made by aggegation apparent on particle diameter increase after, carry out filtering, the solid-liquid separation operation such as centrifugation. As made by aggegation apparent on particle diameter increase method, it is possible to use by carrying out heating and the method for aggegation; Saltout etc. and to use the aggegation method etc. of agglutinant, in these aggegation methods, it may also be useful to the method saltoutd can obtain agglomeration with the short period of time, it is preferred to. As the median size of agglomeration now, it is preferable to 5～100 μm.

Using in the aggegation method saltoutd, such as, it is possible to by by the inorganic salt such as sodium-chlor taking relative to PVDF resin particle 1 mass parts as 0.01～1000 mass parts, be preferably 0.05～500 mass parts about add, thus obtain the agglomeration that particle diameter is big. Specifically, can enumerate in above-mentioned dispersion liquid or suspension, directly add inorganic salt, or add the method for the solution etc. of 0.1～20 mass parts of above-mentioned inorganic salt. As inorganic salt, the inorganic salt such as sodium-chlor, magnesium chloride, calcium chloride, lithium chloride, Repone K, sodium acetate, magnesium acetate, lime acetate, sodium oxalate, magnesium oxalate, caoxalate, Trisodium Citrate, magnesium citrate, citrate of lime can be enumerated. As the solvent making inorganic salt dissolve, it is preferable to water. Expect to add the amount of inorganic salt in particle be more than 0.05 mass parts relative to PVDF resin particle 1 mass parts and for PVDF resin particle is precipitated out poor solvent in saturated meltage below. The PVDF resin particle obtained by the method for present embodiment, by such method aggegation, thus solid-liquid separation becomes easy.

As the method for above-mentioned solid-liquid separation, the methods such as filtration, centrifugation can be enumerated. When filtration, centrifugation, it is possible to use membrane filter (filtration), filter cloth (filtration, centrifugation) etc. As the sieve aperture of strainer, suitably determine according to the granularity of the PVDF resin particle to be obtained, when membrane filter, it is generally about 0.1～50 μm, when filter cloth, it is possible to use Gas permeability during 124.5Pa is 5cm³/cm²The filter cloth of below sec.

The PVDF resin particle obtained like this can be directly used in various purposes, and it maybe can be made to be scattered in desired solvent and make dispersion liquid or make its redispersion make complex body in other medium, and for various purposes.

The PVDF resin particle obtained like this is not substantially below 300nm containing the average primary particle diameter of tensio-active agent, it is more preferable to mode in be the particle of below 200nm. As lower limit, it is about 30nm. In addition, the consistent particle of granularity can be obtained, it is possible to obtain the variation coefficient is less than 40% usually, preferred mode is less than 30%, preferred mode is less than 20%, further preferred mode is less than 18%, it is particularly preferred to mode in be less than 15% PVDF resin particle.

In addition, the average primary particle diameter of so-called PVDF resin particle is determined as follows here: the maximum length measuring 100 particles optionally selected by scanning electron microscope photo, obtains its arithmetical mean, determines.

In addition, represent that the variation coefficient (CV) of homogeneity of the granularity of the PVDF resin particle in present embodiment is by the data of length measurment when calculating average primary particle diameter, is obtained by following formula (1)～formula (3).

(dispersion) formula (1):

X: particle diameter, median size:N: determination data number

(standard deviation) formula (2):

(variation coefficient) formula (3):

PVDF resin particle can be solid can also be hollow, from the such viewpoint of the purposes in industry, it is preferable to solid. In addition, the PVDF resin particle of present embodiment is solid the particulate cross-section of transmission electron microscope can be utilized to confirm.

PVDF resin particle in present embodiment is characterised in that the average primary particle diameter with submicron-scale, narrow diameter distribution, and the packet content that can enumerate tensio-active agent further is few.

With the use of such PVDF resin particle, it is possible to film, porous-film, die surface etc. are applied densely, by the state utilizing this to apply densely, it is possible to formed evenly and the bonding film of thin layer. The tensio-active agent comprised due to this PVDF resin particle is few, and therefore the bonding strength of this bonding film becomes high, useful in industry.

Industrially can utilize to extremely useful in a variety of applications where and practicality by the PVDF resin particle of the method manufacture of present embodiment as this example. specifically, it is possible to use in toning agent additive, the rheology modifier of coating etc., medical-diagnosis checks agent, automotive material, material of construction etc. are to the mechanical characteristics modifying agent of shaping product, film, the mechanical characteristics improvement material of fiber etc., rapid shaping, the resin-formed body raw material of quick manufacture etc., flash distillation molding material, plastisol is with sticking with paste resin, powder adhesion material, the mobility improvement material of powder body, lubricant, rubber ingredients, abrasive, thickening material, filter agent and flocculating aids, jelling agent, agglutinant, additive for coatings, oil absorber, releasing agent, the sliding improving agent of plastic film/sheet, anti blocking agent, gloss conditioning agent, delustring treatment agent, light diffusing agent, surface high rigidity improving agent, toughness improves the various properties-correcting agent such as material, liquid crystal indicator spacer, chromatographic grade fills material, makeup foundation cream base material/additive, microcapsule used additives, the medical material of drug delivery system/diagnosis medicine etc., the retention agent of spices/agricultural chemicals, chemical reaction catalyzer and carrier thereof, adsorbent, Ceramic manufacturing sintering material, the standard particle measuring/analyzing, the particle of field of food industry, powder coating material, electronic photo developing toner etc.

Embodiment

[mensuration of average primary particle diameter]

The average primary particle diameter of the PVDF resin particle in present embodiment is 100 particles selecting optionally to select from the image obtained by NEC scanning electron microscope JEOLJMS-6700F, particle diameter is carried out length measurment as particle diameter by its maximum length, its mean value is set to average primary particle diameter.

[calculating of the variation coefficient of PVDF resin particle]

The variation coefficient (CV) of the PVDF resin particle in present embodiment is the value of each particle diameter using the image obtained from NEC scanning electron microscope JEOLJMS-6700F that the particle diameter of arbitrary 100 is carried out length measurment and obtain, and is obtained by above-mentioned formula (1)～formula (3).

[mensuration of the molecular weight of PVDF resin]

The weight-average molecular weight of PVDF resin uses gel permeation chromatography, carries out contrasting calculating with the calibration curve of polystyrene.

Device: Shimadzu Scisakusho Ltd LC-10A series

Post: Showa Denko K. K GF-7MHQ × 2 piece

Moving phase: dimethyl formamide

Flow: 1.0ml/min

Detection: differential refraction rate meter

Column temperature: 40 DEG C

[mensuration of median size]

Use day machine dress laser diffraction processed/diffuse transmission type particle size distribution device MT3300EXII, use the 0.5 quality % aqueous solution of the withered base phenyl ether of polyoxyethylene (trade(brand)name: ノ Na Le 912A east nation chemical industry system) to measure as dispersion medium. Specifically, the cumulative volume of the particle that will utilize the scattered light of micro-track method parsing laser and obtain, as 100%, obtains summation curve, and the particle diameter (median particle diameter: d50) that this summation curve becomes the point of 50% is set to the median size of particulate.

(embodiment 1)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 7.8g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 534g at 80 DEG C, this solution adds water 66g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously in the particlized groove (receiver) of water 600g of 80 DEG C. This mixed solution adds 10 quality % magnesium acetate aqueous solution 7.8g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 98nm, and the variation coefficient is 14.9%. Show the result in table 1.

[table 1]

(embodiment 2)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 9g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 510g at 80 DEG C, this solution adds water 90g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 9g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 100nm, and the variation coefficient is 15.2%. Show the result in table 1.

(embodiment 3)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 12g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 534g at 80 DEG C, this solution adds water 66g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously the particlized groove of the water 600g of 80 DEG C. This mixed solution adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation. Carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 99nm, and the variation coefficient is 15.4%. Show the result in table 1. In addition, shown in Figure 1 by being observed the image obtained by SEM.

(embodiment 4)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 12g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 534g at 80 DEG C, this solution adds water 66g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously the particlized groove of the water 600g of normal temperature.This mixed solution adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 102nm, and the variation coefficient is 15.1%. Show the result in table 1.

(embodiment 5)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 18g be dissolved in NMP (Northeast chemistry (strain) society system) 510g at 80 DEG C, this solution adds water 90g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously the particlized groove of the water 600g of 80 DEG C. This mixed solution adds 10 quality % magnesium acetate aqueous solution 18g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 105nm, and the variation coefficient is 15.6%. Show the result in table 1.

(embodiment 6)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 103nm, and the variation coefficient is 18.1%. Show the result in table 1.

(embodiment 7)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are dropped to the particlized groove of the mixing solutions comprising methyl alcohol 540g and water 60g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 97nm, and the variation coefficient is 14.4%. Show the result in table 1.

(embodiment 8)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the mixing solutions comprising methyl alcohol 420g and water 180g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 104nm, and the variation coefficient is 15.5%. Show the result in table 1.

(embodiment 9)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the mixing solutions comprising methyl alcohol 300g and water 300gg of normal temperature, this mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, make PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle.Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 107nm, and the variation coefficient is 18.5%. Show the result in table 1.

(embodiment 10)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the mixing solutions comprising methyl alcohol 120g and water 480g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 105nm, and the variation coefficient is 18.5%. Show the result in table 1.

(embodiment 11)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the mixing solutions comprising acetonitrile 30g and water 570g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 109nm, and the variation coefficient is 15.2%. Show the result in table 1.

(embodiment 12)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 300g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 118nm, and the variation coefficient is 16.0%. Show the result in table 1.

(embodiment 13)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 570g at 80 DEG C, this solution adds water 30g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 111nm, and the variation coefficient is 18.2%. Show the result in table 1.

(embodiment 14)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 582g at 80 DEG C, this solution adds water 18g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle.Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 114nm, and the variation coefficient is 18.7%. Show the result in table 1.

(embodiment 15)

Make KF polymkeric substance #8500 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 118nm, and the variation coefficient is 17.3%. Show the result in table 1.

(embodiment 16)

Make KF polymkeric substance #8500 ((strain) Network レ Ha society system) 12g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 80 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 6g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 123nm, and the variation coefficient is 16.6%. Show the result in table 1.

(embodiment 17)

Make KF polymkeric substance #8500 ((strain) Network レ Ha society system) 12g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The above-mentioned solution of 76 DEG C are added into continuously the particlized groove of the water 600g of normal temperature. This mixed solution adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 121nm, and the variation coefficient is 16.3%. Show the result in table 1.

(embodiment 18)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The particlized groove that the above-mentioned solution of 76 DEG C are added into the water 300g of normal temperature continuously, obtains particlized liquid.

Next, while the PVDF resin solution 606g (76 DEG C) adjusted separately and water 300g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 906g (particlized liquid A) from particlized trench bottom. Then, while the PVDF resin solution 606g (76 DEG C) adjusted separately and water 300g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 906g (particlized liquid B) from particlized trench bottom. The particlized liquid (particlized liquid C) remained in particlized groove and particlized liquid A, B add 10 quality % magnesium acetate aqueous solution 6g, make PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle.This filter cake scanning electron microscope (SEM) has been observed, average 1 particle diameter of result particlized liquid A is 120nm, the variation coefficient is 16.6%, average 1 particle diameter of particlized liquid B is 119nm, the variation coefficient is 16.8%, average 1 particle diameter of particlized liquid C is 122nm, and the variation coefficient is 17.0%. Show the result in table 2.

[table 2]

Table 2

(embodiment 19)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The particlized groove that the above-mentioned solution of 76 DEG C are added into the water 200g of normal temperature continuously, obtains particlized liquid.

Next, while the PVDF resin solution 606g (76 DEG C) adjusted separately and water 200g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 806g (particlized liquid A) from particlized trench bottom. Then while the PVDF resin solution 606g (76 DEG C) adjusted separately and water 200g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 806g (particlized liquid B) from particlized trench bottom. The particlized liquid (particlized liquid C) remained in particlized groove and particlized liquid A, B add 10 quality % magnesium acetate aqueous solution 6g, make PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. This filter cake scanning electron microscope (SEM) has been observed, average 1 particle diameter of result particlized liquid A is 121nm, the variation coefficient is 16.8%, average 1 particle diameter of particlized liquid B is 120nm, the variation coefficient is 16.9%, average 1 particle diameter of particlized liquid C is 123nm, and the variation coefficient is 17.2%. Show the result in table 2.

(embodiment 20)

Make KF polymkeric substance #9300 ((strain) Network レ Ha society system) 8.1g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g at 80 DEG C, this solution adds water 60g, produces PVDF resin solution. The particlized groove that the above-mentioned solution of 76 DEG C are added into the 5wt% acetonitrile solution 600g of normal temperature continuously, obtains particlized liquid.

Next, while the PVDF resin solution 608.1g (76 DEG C) adjusted separately and 5wt% acetonitrile solution 600g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 1200g (particlized liquid A) from particlized trench bottom. Then while the PVDF resin solution 606g (76 DEG C) adjusted separately and 5wt% acetonitrile solution 600g (normal temperature) was dripped, with 6 minutes, the speed adding end respectively drop to particlized groove simultaneously, while in the way of keeping the liquid level of particlized liquid, taking out particlized liquid 1200g (particlized liquid B) from particlized trench bottom. The particlized liquid (particlized liquid C) remained in particlized groove and particlized liquid A, B add 10 quality % magnesium acetate aqueous solution 6g, make PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. This filter cake scanning electron microscope (SEM) has been observed, average 1 particle diameter of result particlized liquid A is 123nm, the variation coefficient is 16.9%, average 1 particle diameter of particlized liquid B is 124nm, the variation coefficient is 16.9%, average 1 particle diameter of particlized liquid C is 124nm, and the variation coefficient is 17.0%.Show the result in table 2.

(embodiment 21)

The removable formula flask of 1L adds KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g, acetonitrile (Northeast chemistry (strain) society system) 594g, them are made to dissolve at 80 DEG C, this solution adds water 66.6g, produces PVDF resin solution. The interior pipe of the dual pipe of the outer tube (internal diameter 9.5mm × length 1200mm) of pipe (internal diameter 4mm × length 200mm) and water conveying leads to continuously with the speed of 166.6g/ minute the PVDF resin solution 600g of liquid 76 DEG C within comprising PVDF resin solution and carrying, outer tube led to continuously the water 600g of liquid normal temperature with the speed of 166.6g/ minute, make PVDF resin solution mix with water within the outer tube, produce PVDF resin particle liquid. Particlized liquid adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 88nm, and the variation coefficient is 16.3%. Show the result in table 3.

[table 3]

Table 3

(embodiment 22)

The removable formula flask of 1L adds KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g, acetonitrile (Northeast chemistry (strain) society system) 594g, them are made to dissolve at 80 DEG C, this solution adds water 66.6g, produces PVDF resin solution. The interior pipe of the dual pipe of the outer tube (internal diameter 9.5mm × length 1200mm) of pipe (internal diameter 2mm × length 200mm) and water conveying leads to continuously with the speed of 166.6g/ minute the PVDF resin solution 600g of liquid 76 DEG C within comprising PVDF resin solution and carrying, outer tube led to continuously the water 150g of liquid normal temperature with the speed of 41.7g/ minute, make PVDF resin solution mix with water within the outer tube, produce PVDF resin particle liquid. Particlized liquid adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 81nm, and the variation coefficient is 16.7%. Show the result in table 3.

(embodiment 23)

The removable formula flask of 1L adds KF polymkeric substance #9300 ((strain) Network レ Ha society system) 6g, acetonitrile (Northeast chemistry (strain) society system) 594g, them are made to dissolve at 80 DEG C, this solution adds water 66.6g, produces PVDF resin solution. The interior pipe of the dual pipe of the outer tube (internal diameter 16mm × length 1200mm) of pipe (internal diameter 4mm × length 200mm) and water conveying leads to continuously with the speed of 333g/ minute the PVDF resin solution 600g of liquid 76 DEG C within comprising PVDF resin solution and carrying, outer tube led to continuously the water 600g of liquid normal temperature with the speed of 333g/ minute, make PVDF resin solution mix with water within the outer tube, produce PVDF resin particle liquid. Particlized liquid adds 10 quality % magnesium acetate aqueous solution 12g, makes PVDF resin particle aggegation, carry out with membrane filter filtering, washing, obtain the moisture wet cake of PVDF resin particle. Having been observed by this filter cake scanning electron microscope (SEM), average 1 particle diameter of result is 90nm, and the variation coefficient is 17.2%. Show the result in table 3.

(embodiment 24)

[dissolution process]

The lysate installing stirrer, temperature-indicating instrument and inside in 1L autoclave takes out pipe. Taking out in pipe, be provided with can the pipe connecting of valve opening and closing. In addition, as the receiver of flash distillation crystalline substance analysis, for the autoclave of 1L, the other end (flash distillation crystalline substance precipitates out mouth) of stirrer, condenser, gas ventilation pipe and the pipe connecting from above-mentioned dissolving tank is installed in the position entering into receiver liquid.

In a nitrogen atmosphere, PVDF resin (シ グ マ ア Le De リ ッ チ contract commercial firm system) 18g is dissolved in NMP (Mitsubishi Chemical's (strain) society system) 540g by dissolving tank, adds water 60g at 80 DEG C and adjust PVDF resin solution. Nitrogen is utilized to be forced into 0.5MPa.

[precipitation operation]

The receiver being added with water 600g is stirred, nitrogen has been carried out trace ventilation. Open the valve of the interconnecting pipe of above-mentioned dissolving tank, the PVDF resin solutions of 80 DEG C are moved in the water (normal temperature) of the receiver under liquid to normal atmosphere. Then, flash liquid is added 5 quality % salt solution 40g, stir 30 minutes, carry out with membrane filter filtering, washing, obtain the wet cake of PVDF resin particle. Average primary particle diameter is 103nm, and the variation coefficient is 15.6%. Show the result in table 4.

[table 4]

Table 4

(embodiment 25)

[dissolution process]

The lysate installing stirrer, temperature-indicating instrument and inside in 1L autoclave takes out pipe. Take out in pipe that be provided with can the pipe connecting of valve opening and closing. In addition, as the receiver of flash distillation crystalline substance analysis, for the autoclave of 1L, the other end (flash distillation crystalline substance precipitates out mouth) of stirrer, condenser, gas ventilation pipe and the pipe connecting from above-mentioned dissolving tank is installed in the position entering into receiver liquid.

In a nitrogen atmosphere, PVDF resin ((strain) Network レ Ha society KF polymkeric substance #8500) 12g is dissolved in NMP (Mitsubishi Chemical's (strain) society system) 540g by dissolving tank, adds water 60g and adjust PVDF resin solution at 80 DEG C. Nitrogen is utilized to be forced into 0.5MPa.

[precipitation operation]

The receiver being added with water 600g is stirred, nitrogen has been carried out trace ventilation. Open the valve of the interconnecting pipe of above-mentioned dissolving tank, the PVDF resin solutions of 80 DEG C are moved in the water (normal temperature) of the receiver under liquid to normal atmosphere. Then, flash liquid is added 5 quality % salt solution 40g, stir 30 minutes, carry out with membrane filter filtering, washing, obtain the wet cake of PVDF resin particle. Average primary particle diameter is 101nm, and the variation coefficient is 17.2%. Show the result in table 4.

(embodiment 26)

[dissolution process]

The lysate installing stirrer, temperature-indicating instrument and inside in 1L autoclave takes out pipe. Taking out in pipe, be provided with can the pipe connecting of valve opening and closing. In addition, as the receiver of flash distillation crystalline substance analysis, for the autoclave of 1L, the other end (flash distillation crystalline substance precipitates out mouth) of stirrer, condenser, gas ventilation pipe and the pipe connecting from above-mentioned dissolving tank is installed in the position entering into receiver liquid.

In a nitrogen atmosphere, dissolving tank make PVDF resin ((strain) Network レ Ha society KF polymkeric substance #8500) 12g be dissolved in acetonitrile (Northeast chemistry (strain) society system) 540g, add water 60g at 80 DEG C, adjust PVDF resin solution. Nitrogen is utilized to be forced into 0.5MPa.

[precipitation operation]

The receiver being added with water 600g is stirred, nitrogen has been carried out trace ventilation. Open the valve of the interconnecting pipe of above-mentioned dissolving tank, the PVDF resin solutions of 80 DEG C are moved in the water (normal temperature) of the receiver under liquid to normal atmosphere. Then, flash liquid is added 5 quality % salt solution 40g, stir 30 minutes, carry out with membrane filter filtering, washing, obtain the wet cake of PVDF resin particle. Average primary particle diameter is 105nm, and the variation coefficient is 16.2%. Show the result in table 4.

(comparative example 1)

Make シ グ マ ア Le De リ ッ チ contract commercial firm PVDF resin 18g be dissolved in NMP (Mitsubishi Chemical's (strain) society system) 600g at 80 DEG C, produce PVDF resin dissolves liquid.The particlized groove that the above-mentioned solution of 80 DEG C are added into the water 600g of 80 DEG C continuously, result obtains ropy, can not get particle. Show the result in table 1. In addition, shown in Figure 2 by being observed the image obtained by SEM.

(comparative example 2)

Make KF polymkeric substance #8500 ((strain) Network レ Ha society system) 12g be dissolved in NMP (Northeast chemistry society system) 600g at 80 DEG C, produce PVDF resin solution. The particlized groove that the above-mentioned solution of 80 DEG C are added into the water 600g of normal temperature continuously, result obtains ropy, can not get particle. Show the result in table 1.

Industry utilizability

According to the present invention relates to poly-1, the manufacture method of 1-bis-fluoroethylene resin particle, can easy and manufacture stablely substantially do not contain tensio-active agent, the PVDF resin particle of average 1 below particle diameter 300nm particularly below 200nm, it is provided that widely useful material in industry.

Claims (8)

1. one kind poly-1, the manufacture method of 1-bis-fluoroethylene resin particle, it is characterized in that, implement a1 operation or a2 operation, described a1 operation will comprise poly-the 1 of the organic solvent of 75～99 quality %, the water of 1～25 quality % and 0.5～15 quality % relative to the total amount 100 quality % of organic solvent and water, the solution of 1-bis-fluoroethylene resin is added into poly-1, in the poor solvent of 1-bis-fluoroethylene resin, make poly-1, the operation that 1-bis-fluoroethylene resin particle precipitates out, described a2 operation analyses, by flash distillation crystalline substance, the operation that poly-1,1-bis-fluoroethylene resin particle is precipitated out from described solution.

2. the manufacture method of poly-1,1-bis-fluoroethylene resin particle according to claim 1, implements a1 operation and a2 operation.

3. the manufacture method of poly-1,1-bis-fluoroethylene resin particle according to claim 1 and 2, implements a1 operation continuously.

4. according to arbitrary item of claims 1 to 3 poly-1, the manufacture method of 1-bis-fluoroethylene resin particle, described organic solvent is at least a kind be selected from METHYLPYRROLIDONE, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, 1,3-dimethyl-2-imidazolone and acetonitrile.

5. the manufacture method of poly-1,1-bis-fluoroethylene resin particle according to claim 4, described organic solvent is METHYLPYRROLIDONE or acetonitrile.

6. according to arbitrary item of Claims 1 to 5 poly-1, the manufacture method of 1-bis-fluoroethylene resin particle, the poor solvent of described poly-1,1-bis-fluoroethylene resin is at least a kind be selected from the mixture of the mixture of water, water and acetonitrile, water and methyl alcohol, water and the mixture of ethanol and the mixture of water and propyl alcohol.

7. a poly-1,1-bis-fluoroethylene resin particle, it is characterised in that, average primary particle diameter is more than 30nm and is less than 300nm, and the variation coefficient is less than 20%.

8. poly-1,1-bis-fluoroethylene resin particle according to claim 7, it is not substantially containing tensio-active agent.